Photodissociation Cross Sections Research Articles

Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model

We present a one-dimensional coupled ion-neutral photochemical kinetics and diffusion model to study the atmospheric composition of Titan in light of new theoretical kinetics calculations and scientific findings from the Cassini–Huygens mission. The model extends from the surface to the exobase. The atmospheric background, boundary conditions, vertical transport and aerosol opacity are all constrained by the Cassini–Huygens observations. The chemical network includes reactions between hydrocarbons, nitrogen and oxygen bearing species. It takes into account neutrals and both positive and negative ions with masses extending up to 116 and 74 u, respectively. We incorporate high-resolution isotopic photoabsorption and photodissociation cross sections for N2 as well as new photodissociation branching ratios for CH4 and C2H2. Ab initio transition state theory calculations are performed in order to estimate the rate coefficients and products for critical reactions.Main reactions of production and loss for neutrals and ions are quantitatively assessed and thoroughly discussed. The vertical distributions of neutrals and ions predicted by the model generally reproduce observational data, suggesting that for the small species most chemical processes in Titan’s atmosphere and ionosphere are adequately described and understood; some differences are highlighted. Notable remaining issues include (i) the total positive ion density (essentially HCNH+) in the upper ionosphere, (ii) the low mass negative ion densities (CN−,C3N−/C4H−) in the upper atmosphere, and (iii) the minor oxygen-bearing species (CO2, H2O) density in the stratosphere. Pathways towards complex molecules and the impact of aerosols (UV shielding, atomic and molecular hydrogen budget, nitriles heterogeneous chemistry and condensation) are evaluated in the model, along with lifetimes and solar cycle variations.

Photodissociation of CS from Excited Rovibrational Levels

Abstract Accurate photodissociation cross sections have been computed for transitions from the X 1Σ+ ground electronic state of CS to six low-lying excited electronic states. New ab initio potential curves and transition dipole moment functions have been obtained for these computations using the multi-reference configuration interaction approach with the Davidson correction (MRCI+Q) and aug-cc-pV6Z basis sets. State-resolved cross sections have been computed for transitions from nearly the full range of rovibrational levels of the X 1Σ+ state and for photon wavelengths ranging from 500 Å to threshold. Destruction of CS via predissociation in highly excited electronic states originating from the rovibrational ground state is found to be unimportant. Photodissociation cross sections are presented for temperatures in the range between 1000 and 10,000 K, where a Boltzmann distribution of initial rovibrational levels is assumed. Applications of the current computations to various astrophysical environments are briefly discussed focusing on photodissociation rates due to the standard interstellar and blackbody radiation fields.

Hydrogenated Benzene in Circumstellar Environments: Insights into the Photostability of Super-hydrogenated PAHs

Abstract Polycyclic aromatic hydrocarbons (PAHs), comprised of fused benzene (C6H6) rings, emit infrared radiation (3–12 μm) due to the vibrational transitions of the C–H bonds of the aromatic rings. The 3.3 μm aromatic band is generally accompanied by the band at 3.4 μm assigned to the vibration of aliphatic C–H bonds of compounds such as PAHs with an excess of peripheral H atoms (H n –PAHs). Herein we study the stability of fully hydrogenated benzene (or cyclohexane, C6H12) under the impact of stellar radiation in the photodissociation region (PDR) of NGC 7027. Using synchrotron radiation and time-of-flight mass spectrometry, we investigated the ionization and dissociation processes at energy ranges of UV (10–200 eV) and soft X-rays (280–310 eV). Density Functional Theory (DFT) calculations were used to determine the most stable structures and the relevant low-lying isomers of singly charged C6H12 ions. Partial Ion Yield (PIY) analysis gives evidence of the higher tendency toward dissociation of cyclohexane in comparison to benzene. However, because of the high photoabsorption cross-section of benzene at the C1s resonance edge, its photodissociation and photoionization cross-sections are enhanced, leading to a higher efficiency of dissociation of benzene in the PDR of NGC 7027. We suggest that a similar effect is experienced by PAHs in X-ray photon-rich environments, which ultimately acts as an auxiliary protection mechanism of super-hydrogenated polycyclic hydrocarbons. Finally, we propose that the single photoionization of cyclohexane could enhance the abundance of branched molecules in interstellar and circumstellar media.

A new collocation-based multi-configuration time-dependent Hartree (MCTDH) approach for solving the Schrödinger equation with a general potential energy surface.

We present a new collocation-based multi-configuration time-dependent Hartree (MCTDH) approach for solving the Schrödinger equation required to compute (ro-)vibrational spectra, photodissociation cross sections, reaction rate constants, etc., that can be used with general potential energy surfaces. Collocation obviates the need for quadrature and facilitates using complicated kinetic energy operators. When the basis is good, the accuracy of collocation solutions to the Schrödinger equation is not sensitive to the choice of the collocation points. We test the collocation MCTDH equations we derive by showing that they can be used to compute accurate vibrational energy levels of CH3. It is possible to choose (imaginary) time-independent collocation points with which collocation-based MCTDH energies are accurate. It is therefore not necessary to calculate potential values many times during the propagation.

State-resolved Photodissociation and Radiative Association Data for the Molecular Hydrogen Ion

Abstract We present state-resolved (electronic, vibrational, and rotational) cross sections and rate coefficients for the photodissociation (PD) of and radiative association (RA) of H–H+. We developed a fully quantum mechanical approach within the nonrelativistic Born–Oppenheimer approximation to describe and calculate the data for transitions between the ground electronic state 1 and the 2 , , , , 4 , , , and electronic states (i.e., up to n = 4). Tables of the dipole-matrix elements and energies needed to calculate state-resolved cross sections and rate coefficients will be made publicly available. These data could be important in astrophysical models when dealing with photon wavelengths (or radiation temperature distributions that are weighted toward such wavelengths) around 100 nm. For example, at these wavelengths and a material temperature of 8400 K, the LTE-averaged PD cross section via the (second electronically excited) state is over three times larger than the PD cross section via the (first electronically excited) state.

Behaviour of solid phase ethyl cyanide in simulated conditions of Titan

In order to simulate different altitudes in the atmosphere of Titan, we investigated using infrared spectrometry and mass spectrometry the photochemistry of ethyl cyanide (CH3CH2CN) ices at different temperatures. Heating experiments of the solid phase until complete desorption showed up three phase transitions with a first one appearing to be approximately at the temperature of Titan's surface (94 K), measured by the Huygens probe. Ethyl cyanide, whose presence has been suggested in solid phase in Titan, can be considered as another nitrile for photochemical models of the Titan atmosphere after our first study (Toumi et al., 2016) concerning vinyl cyanide (CH2CHCN). The desorption energy of ethyl cyanide has been calculated to be 36.75 ( ± 0.55) kJ mol−1 using IRTF and mass spectroscopical techniques. High energetic photolysis (λ > 120 nm) have been performed and we identified ethyl isocyanide, vinyl cyanide, cyanoacetylene, ethylene, acetylene, cyanhydric acid and a methylketenimine form as photoproducts from ethyl cyanide. The branching ratios of the primary products were determined at characteristic temperatures of Titan thanks to the value of the νCN stretching band strength of ethyl cyanide that has been calculated to be 4.12 × 10−18 cm molecule−1. We also report here for the first time the values of the photodissociation cross sections of C2H5CN for different temperatures.

Photodissociation and photoionisation of atoms and molecules of astrophysical interest

A new collection of photodissociation and photoionisation cross sections for 102 atoms and molecules of astrochemical interest has been assembled, along with a brief review of the basic processes involved. These have been used to calculate dissociation and ionisation rates, with uncertainties, in a standard ultraviolet interstellar radiation field (ISRF) and wavelength-dependent radiation fields. The new ISRF rates generally agree within 30% with our previous compilations, with a few notable exceptions. The reduction of rates in shielded regions was calculated as a function of dust, molecular and atomic hydrogen, atomic C, and self-shielding column densities. The relative importance of shielding types depends on the species in question and the dust optical properties. The new data are publicly available from the Leiden photodissociation and ionisation database. Sensitivity of rates to variation of temperature and isotope, and cross section uncertainties, are tested. Tests were conducted with an interstellar-cloud chemical model, and find general agreement (within a factor of two) with the previous iteration of the Leiden database for the ISRF, and order-of-magnitude variations assuming various kinds of stellar radiation. The newly parameterised dust-shielding factors makes a factor-of-two difference to many atomic and molecular abundances relative to parameters currently in the UDfA and KIDA astrochemical reaction databases. The newly-calculated cosmic-ray induced photodissociation and ionisation rates differ from current standard values up to a factor of 5. Under high temperature and cosmic-ray-flux conditions the new rates alter the equilibrium abundances of abundant dark cloud abundances by up to a factor of two. The partial cross sections for H2O and NH3 photodissociation forming OH, O, NH2 and NH are also evaluated and lead to radiation-field-dependent branching ratios.

BEAMDB and MolD – databases for atomic and molecular collisional and radiative processes: Belgrade nodes of VAMDC

We present two atomic and molecular (A&M) databases, MolD and BEAMDB, hosted by the SerVO – the Serbian virtual observatory ( http://servo.aob.rs ). These databases and web applications have been implemented in accordance to the standards developed by Virtual Atomic and Molecular Data Centre (VAMDC, http://www.vamdc.eu ). The MolD database contains photo-dissociation cross-sections for individual rovibrational states of the diatomic molecular ions and rate coefficients for the atom-Rydberg atom chemi-ionisation and inverse electron-ion-atom chemi-recombination processes. The Belgrade electron/atom(molecule) database (BEAMDB) provides collisional data for electron interactions with atoms and molecules. Differential cross sections (DCS) are presented for both elastic and inelastic (excitation) cross sections in tabulated data tables. These DCS data are integrated over a full range of scattering angles in order to achieve integral, momentum transfer and viscosity cross sections as functions of impact electron energy. Beside these tables, energy loss spectra are presented in the graphical form.

The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium.

The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross section of HCN and HNC isomers have been calculated in the 7-13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differences with respect to the experimental one, and this is attributed to the need of considering non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental one. It is found that HNC is photodissociated faster than HCN by a factor of 2.2, for the local interstellar radiation field, and 9.2, for the solar radiation field at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field it is necessary to use different photodissociation rates for each of the two isomers, obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.

A study of the valence shell absolute photoabsorption, photoionisation and photodissociation cross sections and the photoionisation quantum efficiency of carbonyl sulphide

The absolute photoabsorption, photoionisation and photodissociation cross sections and the photoionisation quantum efficiency of carbonyl sulphide have been measured using a double ion chamber and synchrotron radiation in the energy range from the ionisation threshold to 24eV. In addition to the absorption bands associated with well established Rydberg series, some previously unassigned features have been tentatively attributed to an f-type Rydberg series converging onto the B̃2Σ+ state ionisation threshold. Structure appearing in the photodissociation spectrum has been correlated with that observed in earlier fluorescence yields for emission, due mainly to the CS photofragment, occurring between 160 and 300nm. The photoionisation quantum efficiency reaches a plateau value close to unity for energies above ∼16eV. The predissociation of Rydberg states into neutral fragments does not appear to affect the photoionisation quantum efficiency of carbonyl sulphide to the extent that is commonly observed in other small molecules. A sum rule analysis has been carried out by combining the present absolute photoabsorption measurements with similar data covering the remaining energy regions.

Rovibrationally resolved photodissociation of SH+

Photodissociation cross sections for the SH+ radical are computed from all rovibrational (RV) levels of the ground electronic state for wavelengths from threshold to 500 Å. The five electronic transitions, , , and , are treated with a fully quantum–mechanical two-state model, i.e. nonadiabatic couplings between excited states were not included. The photodissociation calculations incorporate adiabatic potentials and transition dipole moment functions computed in the multireference configuration interaction approach along with the Davidson correction (MRCI+Q), but adjusted to match available experimental molecular data and asymptotic atomic limits. Local thermodynamic equilibrium (LTE) photodissociation cross sections were computed which assume a Boltzmann distribution of RV levels in the molecular state of the SH+ cation. The LTE cross sections are presented for temperatures in the range 1000–10 000 K. Applications of the current photodissociation cross sections to interstellar gas, photon-dominated regions, and stellar atmospheres are briefly discussed.

Photochemistry of forbidden oxygen lines in the inner coma of 67P/Churyumov-Gerasimenko.

Observations of the green and red‐doublet emission lines have previously been realized for several comets. We present here a chemistry‐emission coupled model to study the production and loss mechanisms of the O(1S) and O(1D) states, which are responsible for the emission lines of interest for comet 67P/Churyumov‐Gerasimenko. The recent discovery of O2 in significant abundance relative to water 3.80 ± 0.85% within the coma of 67P has been taken into consideration for the first time in such models. We evaluate the effect of the presence of O2 on the green to red‐doublet emission intensity ratio, which is traditionally used to assess the CO2 abundance within cometary atmospheres. Model simulations, solving the continuity equation with transport, show that not taking O2 into account leads to an underestimation of the CO2 abundance within 67P, with a relative error of about 25%. This strongly suggests that the green to red‐doublet emission intensity ratio alone is not a proper tool for determining the CO2 abundance, as previously suggested. Indeed, there is no compelling reason why O2 would not be a common cometary volatile, making revision of earlier assessments regarding the CO2 abundance in cometary atmospheres necessary. The large uncertainties of the CO2 photodissociation cross section imply that more studies are required in order to better constrain the O(1S) and O(1D) production through this mechanism. Space weather phenomena, such as powerful solar flares, could be used as tools for doing so, providing additional information on a good estimation of the O2 abundance within cometary atmospheres.

MOL-D: A Collisional Database and Web Service within the Virtual Atomic and Molecular Data Center

MOL-D database is a collection of cross-sections and rate coefficients for specific collisional processes and a web service within the Serbian Virtual Observatory (SerVO) and the Virtual Atomic and Molecular Data Center (VAMDC). This database contains photo-dissociation cross-sections for the individual ro-vibrational states of the diatomic molecular ions and rate coefficients for the atom-Rydberg atom chemi-ionization and inverse electron-ion-atom chemi-recombination processes. At the moment it contains data for photodissociation cross-sections of hydrogen H2+ and helium He2+ molecular ions and the corresponding averaged thermal photodissociation cross-sections. The ro-vibrational energy states and the corresponding dipole matrix elements are provided as well. Hydrogen and helium molecular ion data are important for calculation of solar and stellar atmosphere models and for radiative transport, as well as for kinetics of other astrophysical and laboratory plasma (i.e. early Universe).

Photodissociation of the carbon monoxide dication in the (3)Σ(-) manifold: Quantum control simulation towards the C(2+) + O channel.

The photodissociation and laser assisted dissociation of the carbon monoxide dication X(3)Π CO(2+) into the (3)Σ(-) states are investigated. Ab initio electronic structure calculations of the adiabatic potential energy curves, radial nonadiabatic couplings, and dipole moments for the X (3)Π state are performed for 13 excited (3)Σ(-) states of CO(2+). The photodissociation cross section, calculated by time-dependent methods, shows that the C(+) + O(+) channels dominate the process in the studied energy range. The carbon monoxide dication CO(2+) is an interesting candidate for control because it can be produced in a single, long lived, v = 0 vibrational state due to the instability of all the other excited vibrational states of the ground (3)Π electronic state. In a spectral range of about 25 eV, perpendicular transition dipoles couple this (3)Π state to a manifold of (3)Σ(-) excited states leading to numerous C(+) + O(+) channels and a single C(2+) + O channel. This unique channel is used as target for control calculations using local control theory. We illustrate the efficiency of this method in order to find a tailored electric field driving the photodissociation in a manifold of strongly interacting electronic states. The selected local pulses are then concatenated in a sequence inspired by the "laser distillation" strategy. Finally, the local pulse is compared with optimal control theory.

Photodissociation spectroscopy of the dysprosium monochloride molecular ion.

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl(+). The photodissociation cross section for the photon energy range 35,500 cm(-1) to 47,500 cm(-1) is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43,000 cm(-1). The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl(+) is extremely complex due to the presence of multiple open electronic shells, including the 4f(10) configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy(+) ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.

SOLAR SPECTRAL IRRADIANCE, SOLAR ACTIVITY, AND THE NEAR-ULTRA-VIOLET

The previous calculations of the Solar Spectral Irradiance (SSI) by the Solar Radiation Physical Modeling, version 2 system, are updated in this work by including new molecular photodissociation cross-sections of important species, and many more levels and lines in its treatment of non-LTE radiative transfer. The current calculations including the new molecular photodissociation opacities produce a reduced over-ionizaton of heavy elements in the lower chromosphere and solve the problems with prior studies of the UV SSI in the wavelength range 160–400 nm and now reproduce the available observations with much greater accuracy. Calculations and observations of the near-UV at 0.1 nm resolution and higher are compared. The current set of physical models includes four quiet-Sun and five active-region components, from which radiance is computed for ten observing angles. These radiances are combined with images of the solar disk to obtain the SSI and Total Solar Irradiance and their variations. The computed SSI is compared with measurements from space at several nm resolution and agreement is found within the accuracy level of these measurements. An important result is that the near-UV SSI increase with solar activity is significant for the photodissociation of ozone in the terrestrial atmosphere because a number of highly variable upper chromospheric lines overlap the ozone Hartley band.

Nonuniversal BBN bounds on electromagnetically decaying particles

In Poulin and Serpico [Phys. Rev. Lett. 114, 091101 (2015)] we recently argued that when the energy of a photon injected in the primordial plasma falls below the pair-production threshold the universality of the nonthermal photon spectrum from the standard theory of electromagnetic cascades onto a photon background breaks down. We showed that this could reopen or widen the parameter space for an exotic solution to the ``lithium problem.'' Here we discuss another application, namely the impact that this has on nonthermal big bang nucleosynthesis constraints from $^{4}\mathrm{He}$, $^{3}\mathrm{He}$, and $^{2}\mathrm{H}$, using the parametric example of monochromatic photon injection of different energies. Typically, we find tighter bounds than those existing in the literature, up to more than 1 order of magnitude. As a consequence of the nonuniversality of the spectrum, the energy dependence of the photodissociation cross sections is important. We also compare the constraints obtained with current level and future reach of cosmic microwave background spectral distortion bounds.

Quantum and classical non-adiabatic dynamics of LiNe photodissociation

The 3D photodissociation dynamics of LiNe system is investigated by quantum calculations using the multi-configuration time-dependent Hartree (MCTDH) method and by classical simulations with the trajectory surface hopping (TSH) approach. Six electronic states of A’ symmetry and two states of A” symmetry are involved in the process. Couplings in the excitation region and two conical intersections in the vicinity of the Franck–Condon zone control the non-adiabatic nuclear dynamics. A diabatic representation including all the states and the couplings is determined. Diabatic and adiabatic populations calculated for initial excitation to pure diabatic and adiabatic states lead to a clear understanding of the mechanisms governing the non-adiabatic photodissociation process. The classical and quantum photodissociation cross-sections for absorption in two adiabatic states of the A’ symmetry are calculated. A remarkable agreement between quantum and classical results is obtained regarding the populations and the absorption cross-sections.

Visible spectrum photofragmentation of O₃⁻(H₂O)n, n ≤ 16.

Photofragmentation of ozonide solvated in water clusters, O3(-)(H2O)n, n ≤ 16, has been studied as a function of photon energy as well as the degree of solvation. Using mass selection, the effect of the presence of the solvent molecule on the O3(-) photodissociation process is assessed one solvent molecule at a time. The O3(-) acts as a visible light chromophore within the water cluster, namely the O3(-)(H2O) total photodissociation cross-section exhibits generally the same photon energy dependence as isolated O3(-) throughout the visible wavelength range studied (430-620 nm). With the addition of a single solvent molecule, new photodissociation pathways are opened, including the production of recombined O3(-). As the degree of solvation of the parent anion increases, recombination to O3(-)-based products accounts for close to 40% of photoproducts by n = 16. The remainder of the photoproducts exist as O(-)-based; no O2(-)-based products are observed. Upper bounds on the O3(-) solvation energy (530 meV) and the O(-)-OO bond dissociation energy in the cluster (1.06 eV) are derived.

Action spectroscopy of SrCl⁺ using an integrated ion trap time-of-flight mass spectrometer.

The photodissociation cross-section of SrCl(+) is measured in the spectral range of 36,000-46,000 cm(-1) using a modular time-of-flight mass spectrometer (TOF-MS). By irradiating a sample of trapped SrCl(+) molecular ions with a pulsed dye laser, X(1)Σ(+) state molecular ions are electronically excited to the repulsive wall of the A(1)Π state, resulting in dissociation. Using the TOF-MS, the product fragments are detected and the photodissociation cross-section is determined for a broad range of photon energies. Detailed ab initio calculations of the SrCl(+) molecular potentials and spectroscopic constants are also performed and are found to be in good agreement with experiment. The spectroscopic constants for SrCl(+) are also compared to those of another alkaline earth halogen, BaCl(+), in order to highlight structural differences between the two molecular ions. This work represents the first spectroscopy and ab initio calculations of SrCl(+).